Premium
Electron transfer between biphenyl and biphenyl anion radicals: Reorganization energies and electron transfer matrix elements
Author(s) -
Li XiangYuan,
He FuCheng
Publication year - 1999
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(19990430)20:6<597::aid-jcc5>3.0.co;2-c
Subject(s) - biphenyl , electron transfer , radical , ion , chemistry , electron , matrix (chemical analysis) , photochemistry , physics , organic chemistry , nuclear physics , chromatography
Intermolecular electron transfer (ET) between the parallel benzene anion radical and neutral benzene is studied at the UHF/4‐31G level. It is found that the diabatic activation energy remains almost invariant (14.2 kJ mol −1 ) when d , the distance between the two parallel benzene rings, is >0.45 nm. The exponential fall‐off of the ET matrix element, V rp , with d is examined. On the basis of the calculated results of the ET matrix element for the system of two parallel benzenes, it is concluded that direct calculation of the ET matrix element, based on the two‐state model, is more accurate than that based on the Koopmans theorem. Ab initio calculations are performed in the investigation of the ET reaction between biphenyl anion radical and neutral biphenyl. By using the Dunning's (9s, 5p)/(3s, 2p) basis set with polarization functions on all atoms (DZP), the reorganization energy for the gas phase intermolecular ET is shown to be 109.2 kJ mol −1 . Using the UHF/STO‐3G method and direct calculation of the two‐state model, V rp values of 2.055 kJ mol −1 and 0.429 kJ mol −1 are obtained for cyclohexylenyl‐ and decalenyl‐mediated ET systems. When we use the Koopmans theorem instead of the direct calculation, these V rp values are shown to be 1.55 kJ mol −1 and 0.326 kJ mol −1 for the two corresponding systems, respectively. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 597–603, 1999